IL22234A - Thermoplastic composition - Google Patents
Thermoplastic compositionInfo
- Publication number
- IL22234A IL22234A IL22234A IL2223464A IL22234A IL 22234 A IL22234 A IL 22234A IL 22234 A IL22234 A IL 22234A IL 2223464 A IL2223464 A IL 2223464A IL 22234 A IL22234 A IL 22234A
- Authority
- IL
- Israel
- Prior art keywords
- mole
- polyesteramide
- melting point
- polyoxymethylene
- following
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 15
- 229920001169 thermoplastic Polymers 0.000 title claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 46
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- -1 polyoxymethylenes Polymers 0.000 description 44
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 34
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 24
- 229920006324 polyoxymethylene Polymers 0.000 description 24
- 229930040373 Paraformaldehyde Natural products 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 235000011037 adipic acid Nutrition 0.000 description 17
- 239000001361 adipic acid Substances 0.000 description 17
- 239000004615 ingredient Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QIEFMYFGTMMHEN-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(2-methylcyclohexyl)phenyl]methyl]-4-methyl-6-(2-methylcyclohexyl)phenol Chemical compound CC1CCCCC1C1=CC(C)=CC(CC=2C(=C(C3C(CCCC3)C)C=C(C)C=2)O)=C1O QIEFMYFGTMMHEN-UHFFFAOYSA-N 0.000 description 1
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- OWEZJUPKTBEISC-UHFFFAOYSA-N decane-1,1-diamine Chemical compound CCCCCCCCCC(N)N OWEZJUPKTBEISC-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
This invention relates to the stabilisation of polyoxymethylenes against degradation.
Polyoxymethylenes are a group of thermoplastic resins with very advantageous mechanical properties containing structural units of the formula:- C- 0 - CH2 -]n where n is an integer. These resin are however, subject to degradation, particularly under the influence of heat and the degradation processes may be divided up into three different groups :- a) Degradation of the chain ends with liberation of gaseous formaldehyde. To obviate this degradation which takes place largely under the influence of heat, it has been shown that the presence of an ether or ester group at the end of chain prevents this degradation; b) Oxidation of the chains: the polyoxymethylene chains are readily oxidisable and they may be protected from this by the addition of anti-oxidants to the compositions. These anti-oxidants generally contain phenolic or amino groups; c) Cleavage of the chains: the chains may cleave and then also liberate formaldehyde from the cleaved ends. To obviate this, it has been proposed to add "formaldehyde acceptors". The function of these additives is to prevent degradation of polyoxymethylenes during its processing in the hot state. These additives are used in conjunction with the anti-oxidants discussed above and together with ester or ether terminated chains.
Various additives have been proposed to prevent the degradation of the polyoxymethylenes, particularly as the diamide of malonic acid, polymethacrylic amides, methyl and methacrylic amide methacrylate copolymers, and polyamides of the type obtained by the condensation of the following amines and acids : 1,1,6,6 tetramethylhexamethylene diamine/adipic acid 2,11 diaminodecane/2-2-5-5 tetr'amethyladipic acid 2,5 dimethylpiperazine/glutaric acid 2,5 dimethylpiperazine/suberic acid bis-3 aminopropylether/adipic acid 38% polycaprolactam, 35% polyhexamethylene adipamide/ 27% polyhexamethylene sebacamide terpolymer.
However, these additives are not capable of being used widely unless they satisfy a number of conditions, viz : - the absence of toxicity; - a high insolubility in conventional solvents; more particularly water and stability in respect of hydrolysis ; - ease of use; in particular, an additive in an extremely divided form results in good easy homogenisation with the polyoxymethylene powder with little expense; and because of the good dispersion the finished articles tend to have no stains.
According to the present invention, we provide a thermoplastic composition which comprises a mixture of a polyoxymethylene and a polyesteramide. Preferably, the polyesteramide should constitute from 0.8 to 5% by weight on the polyoxymethylene. These polyesteramides are excellent "formaldehyde acceptors".
The production of polyesteramides is already polyesteramid.es, reference may be made to the "Journal of Polymer Science" 61, (1962), 353-359, J.L.R. Williams, Laakso and Contois L,E, The polyesteramide is formed by the reaction of a diacid with a diamine, amino acid or the corresponding lactams and a diol or aminoalcohol.
If the amount of polyesteramide used is less than 0.8%, the maximum effects of the polyesteramide are not obtained, and if used in excess of 5 , the mechanical properties of the final polymer may be impaired.
All the polyesteramides used according to the invention may contain aliphatic, aromatic or cycloalkane groups. The polyesteramides with a melting point between 120° and 230°C are the most advantageous.
According to one aspect of the invention, the polyesteramide contains groups derived from caprolactam. Such polyesteramides are produced by adding caprolactam to the reaction mixture from which the polyesteramide is to be obtained. These caprolactam-based polyesteramides are more easily dispersed and used in the polyoxymethylene , and furthermore, they also improve the injection and extrusion properties of the stabilised polyoxymethylene.
The most preferred polyesteramides are those having the formula : - £0C-R-C0NH-(CH2)m-H CO„-R-CO-O-C„CH2 n-0-CO_-E ' -C0NH-(CHd)p-NH Co-a-co-o- cti*)^- o-Jx where m, n, p_ are integers in the range of from 1 to 12 and.R is hydrocarbon radical, such as alkyl or phenyl groups; this radical may differ from one polymer chain to another, and x is an integer.
Of these polyesteramides the most favoured are a) m n = p = 6 b) m p = 6, n = 10 m P = 6 c) n 6 for one half of the long chain, and n 10 for the other half, substance (c) being a copolymer.
The preferred polyesteramides , may be prepared by transesterifying a diester-diamide of the formula with a glycol of formula H0-(GH2)n-0H in the presence of a transesterification catalyst.
The value of the number n may be varied within the polyesteramide molecule by suitable choice of the glycol. This transesterification process gives copolyme: with certain physical properties - more particularly the melting point - differing from one another as required.
The stabilised polyoxymethylenes not only have excellent stability but also a good surface gloss.
In order that the invention may be more fully understood, the following Examples are given by way of illustration only.
Example I ; The following reactants were heated together in a neutral atmosphere in a stainless-steel autoclave at temperatures of 270-290°C for 2-3 hours at a pressure of 18 kg/cm . After which the reaction was concluded in vacuo (0.5 mm Hg) for 1-2 hours and the product removed from the reactor. The ingredients 0.75 mole of hexane diammonium adipate 0.25 mole of adipic acid Ο.25 mole of ethylene glycol The resultant polyesteramide had the following characteristics : - Melting point - 220° to 222°C Intrinsic viscosity ^ 0.42.
Example II; Using the same procedure as in Example I, but with the following ingredients :- 0,65 mole of hexane diammonium adipate 0.35 mole of adipic acid 0.35 mole 1-6 hexanediol A polyesteramide having the following characteristics :- Melting point - 220°C Intrinsic viscosity ^ 0.45 was obtained.
Example III; Using the same procedure as in Example I, but with the following ingredients :- 0.75 mole of hexane diammonium adipate Ο.25 mole of adipic acid Ο.25 mole of 1-6 hexanediol A polyesteramide having the following characteristics :- Melting point - 220°-225°C Viscosity 0.42 was obtained.
Example IV; Using the same procedure as in Example I, but 0.75 mole of hexane diammonium adipate 0.25 mole of adipic acid Ο.25 mole of 1-10 decanediol A polyesteramide having the following characteristics :- Melting point - 225°C Viscosity ^ 0.62 was obtained.
Example V: Using the same- procedure as in Example I, "but with the following ingredients : - 1.1 mole of hexane diammonium adipate Ο.5 mole of adipic acid Ο.5 mole of ethyleneglycol 1.1 mole of caprolactam , A polyesteramide having the following characteristics Melting point - 180°C Viscosity ^ 0.42 was obtained.
Example VI: Using the same procedure as in Example I, but with the following ingredients :- 0.5 mole of hexane diammonium adipate 0,25 mole of adipic acid Ο.25 mole of 1-6 hexanediol 0,5 mole of caprolactam A polyesteramide having the following characteristics : - Melting point - 170°C Viscosity 0,39 Example VII; Using the same procedure as in Example I, hut with the following ingredients : - 1,1 mole of hexane diammonium adipate 0.5^ mole of adipic acid 0,5-4- mole of 1-10 decanediol 1.1 mole of caprolactam A polyesteramide having the following characteristics :- Melting point - 177-180°C Viscosity ^ 0,65 was' ohtained.
Example VIII: Using the same procedure as in Example I, but with the following ingredients : - 0,25 mole of hexane diammonium adipate 0,25 mole of adipic acid 0,25 mole of 1-6 hexanediol 1 mole of caprolactam A polyesteramide having the following characteristics :- Melting point - 130°C Viscosity ^ 0.41 was obtained.
Example IX; Using the same procedure as in Example I, but with the following ingredients :- 0.82 mole of adipic acid 0.82 mole of 1-6 hexanediol 4.6 mole of caprolactam Melting point - 162°-165°C Viscosity ^ 0,45 was obtained.
Example X; Using the same procedure as in Example I, hut with the following ingredients : - 1.1 mole of hexane diammonium adipate 0.54 mole of adipic acid 0.54 mole of 1-6 hexanediol 1.1 mole of aminocaproic acid A polyesteramide having the following characteristics :- Melting point - 185°C.
Viscosity ^ 0.48 was obtained.
Example XI: Using the same procedure as in Example I, but with the following ingredients : - 1.57 mole of hexane diammonium adipate 0.58 mole of adipic acid 0.58 mole of 1-10 decanediol 0.56 mole of aminocaproic acid A polyesteramide having the following characteristics :- Melting point - 220°C Viscosity ^ 0.60 was obtained.
Example XII: Using the same procedure as in Example I, but with the following ingredients : - 0.25 mole of hexane diammonium adipate 0.25 mole of adipic acid 0,25 mole of 1-4 cyclohexanedimethanol 1 mole of £ caprolactam polyesteramide having the following characteristics : - Melting point - 120°C Viscosity 0.42 was obtained.
Example XIII: Using the same procedure as in Example I, but with the following ingredients :- 0.75 mole of hexane diammonium adipate Ο.25 mole of adipic acid Ο.25 mole of 1-4 cyclohexanedimethanol A polyesteramide having the following characteristics :- Melting point - 210°G Viscosity ^ 0.44 was obtained.
Example XIV; Using the same procedure as in Example I, but with the following ingredients :- Ο.25 mole of hexane diammonium adipate Ο.25. mole of adipic acid 0,25 mole of 1-10 decanediol 1 mole of £ caprolactam A polyesteramide having the following characteristics : - Melting point - 150°C Example XV: Using the same procedure as in Example I, but with the following ingredients : - 0,25 mole of hexane diammonium adipate Ο.25 mole of hexane diammonium sebacate Ο.25 mole of 1-10 decanediol Ο.25 mole of adipic acid 0.5 mole of £ caprolactam A polyesterami.de having the following characteristics :- Melting point - 1 5°C Viscosity ^ 0.58 was obtained.
Example XVI: Using the same procedure as in Example I, but with the following ingredients : - 0.5 mole of hexane diammonium adipate Ο.25 mole of sebacic acid 0,25 mole of 1-10 decanediol 0.5. mole of , caprolactam A polyesteramide having the following characteristics : - Melting point - 15 °C Viscosity ^ 0.55 was obtained.
The various polyesteramides were used for the stabilisation of polyoxymethylenes in various proportions .
The polyoxymethylene used in these tests was prepared by irradiation and polymerisation of solid .
This polyoxymethylene was then treated in accordance with the process described in French Patent Specification No. 1 , 333 , 327. The polyoxymethylene thus treated has an intrinsic viscosity of = 0.6. 0.5% of 1-1 bis (4 , 2- hydroxy- -methyl tertiobutylphenyl) butane (a phenolic- type anti-oxidant) was then added to the composition.
To assess the stability of the final products the resin compositions were heated at 222°C for ·¾· hour, 1 hour and 2 hours respectively and the amount of product lost was determined at the end of each of these periods .
The following table shows the results with the various compounds obtained with the polyesteramides produced in each of the Examples.
Additive % of % loss % loss % loss ("by Example additive 222°C 222°C 222°C No.) added after after after min 60 min 120 min Control 0 2.7 6.8 23 Example I 1.5 0.4 1.2 5 Example II 1.5 0.9 2.5 7.1 Example III 1.5 0.8 2.3 7.0 Example IV 1.5 0.4 2.0 7.0 Example V 1.5 0.4 0.96 3.98 Example VI 1.5 0.53 1.4 6.0 2 0.34 1.2 5.12 Example VII 2 0.33 1.0 5.3 Example VIII 1.5 0.55 1.78 5.36 2 0.32 1.01 4.9 Example IX 2 0.76 1.94 6.8 Example X 1.5 0.39 1.42 6.7 2 0.3 1.2 5 Example XI 1.5 0.45 1.57 7.05 2 0.38 1.49 6.29 Example XII 2 0.35 1.3 5.5 Example XIII 2 0.4 1.45 6.9 Example XIV 2 0.42 1.65 7.5 Example XV 2 0.45 1.8 7.9 3 0.39 1.4 6.5 Example XVI 2 0.4 1.65 7.7 3 0.3 1.45 6.6 To assess the above results, the following tahle gives the values obtained under the same conditions with various known additives.
Additive % of % loss % loss % loss additive 222°C 222°C 222°C added after after after min 60 min 120 min Malonamide 2 1.2 4.1 13.1 Urea 2 1.3 5.1 15 Terpolymer : 38% polycaprolactam % polyhexamethylene adipamide/27% poly-hexamethylene-sebacamide 2 0.9 2.7 8.2 A comparison of these tables shows the superior results obtained with the polyesteramide additives.
Other tests were carried out with certain polyesteramides and the thermal stability of the polyoxymethylene compounds obtained was measured by the following test:- 0.2 g. of the product undergoing test (stabilised polyoxymethylene) was placed in a test-tube which was then fitted in the inner casing of a thermostatic jacket; this inner casing was 22 cm. long and had an inside diameter of 2.8 cm. The temperature of the jacket was set to 222°C by boiling methyl salicylate. During the measurement the test-tube containing the product (length 100 mm., outside diameter 10 mm., inside diameter 8 mm.), of pyrex glass, was held in a vertical position inside the jacket by a metal coil suspended from the jacket , plug, its bottom end being 2 cm. above the bottom of the casing. Half an hour after the test-tube had been fitted in the inner casing of the jacket the test-tube was withdrawn and the loss of weight was measured.
The loss per minute for 100 g. of the product was calculated and this calculated value S has been given below in Examples XVII to XXI for the various products under test.
The gloss of the final products obtained was also measured with a "Gardner Gloss Meter". This meter is specially designed for this purpose and complies with the American ASTM Standard D 523-53 T; the gloss was measured by this method at an incidence of 60° (B 60 value indicated below) and an incidence of ° (B 5 value below).
The polyoxymethylene treated in these Examples was the same as that treated in the above examples.
The anti-oxidant used was 0.5% of bis-[2-hydroxy-3-(methyl-2-cyclohexyl)-5-methylphenyl] methane.
In the following Examples a polyesteramide of the following formula was used:- £0C-R-C0NH-(CH ) - CH ) - H where R, m, n and p_ are as stated in the Examples.
Example XVII: The polyoxymethylene contained 1% of the polyesteramide where :- m = n = p = 6, and E is a para-disubstituted phenyl radical.
The following results were obtained :- S = 0.03 B 60 = 6,2 B 5 = 9.0 Example XVIII; Using the same treated polyoxymethylene containing 1.5% of polyesteramide wherei :- m = p = 6 = The following results were obtained :- S = 0.027 B 60 = 6.0 B 4-5 = 8.6.
Example XIX; Using the same treated polyoxymethylene containing 1.5% of a polyesteramide copolymer wherein :- m = p = 6 n = 6 n = 10 (half the total quantity of glycol was used with n =_6 and the other half with n = 10) and R is a para-disubstituted phenyl radical.
The following results were obtained :- S = 0.03 B 60 = 6.3 B -5 = 9.4·.
Example XX: The same polyoxymethylene was used with an addition of a polyesteramide obtained by the action of the following diesterdiamide on glycol :-C^-O-CO-(CH2)^-CO-WH-(CH2)2-NH-C0-(CH2^-COOC^ The melting point of this polyesteramide was 170°C and its viscosity was °· ·· The addition of 2% of this polyesteramide to the polyoxymethylene gave a composition with a loss at 222°C as follows :- After 30 minutes: 0.6% 60 " 1.9% » 120 " 8 % Example XXI: Using the same treated polyoxymethylene containing 1.5% of the polyamide formed by the terpolymer: 38% polycaprolactam, 35% polyhexamethylene adipamide/27% polyhexamethylene sebacimide, the following results were obtained S = 0.03 B 60 = 4.9 B 5 = 7.3.
The values for this latter example are similar to those given by commercial polyoxymethylene compositions.
Claims (1)
1. Claim 1 substantially as herein described in any of Examplee XVII to Dated this 11th day of S3 insufficientOCRQuality
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR950859A FR1379756A (en) | 1963-10-17 | 1963-10-17 | Improved process for stabilizing polyoxymethylenes |
| FR978012A FR1406658A (en) | 1963-10-17 | 1964-06-12 | Process for stabilizing polyoxymethylenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IL22234A true IL22234A (en) | 1968-02-26 |
Family
ID=26203927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL22234A IL22234A (en) | 1963-10-17 | 1964-10-12 | Thermoplastic composition |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3355514A (en) |
| BE (1) | BE653912A (en) |
| CH (1) | CH442743A (en) |
| DE (1) | DE1250120B (en) |
| FR (2) | FR1379756A (en) |
| GB (1) | GB1019786A (en) |
| IL (1) | IL22234A (en) |
| LU (1) | LU47075A1 (en) |
| NL (1) | NL141224B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459709A (en) * | 1965-07-02 | 1969-08-05 | Sir Soc Italiana Resine Spa | Method of stabilizing polyoxymethylenes |
| IT1006136B (en) * | 1973-12-28 | 1976-09-30 | Sir Soc Italiana Resine Spa | STABILIZATION OF ACETAL POLYMERS |
| US3960984A (en) * | 1974-04-16 | 1976-06-01 | E. I. Du Pont De Nemours And Company | Composition of oxymethylene polymer and amide oligomers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235624A (en) * | 1962-12-04 | 1966-02-15 | Tenneco Chem | Stabilized polyoxymethylene compositions |
| US3288885A (en) * | 1963-04-04 | 1966-11-29 | Tenneco Chem | Composition for stabilizing polyacetals comprising (1) nu-acyl-p-aminophenol, (2) a superpolyamide, and (3) a diester of a thiodialkanoic acid |
-
0
- DE DENDAT1250120D patent/DE1250120B/en active Pending
-
1963
- 1963-10-17 FR FR950859A patent/FR1379756A/en not_active Expired
-
1964
- 1964-06-12 FR FR978012A patent/FR1406658A/en not_active Expired
- 1964-10-02 BE BE653912D patent/BE653912A/xx unknown
- 1964-10-03 LU LU47075A patent/LU47075A1/xx unknown
- 1964-10-12 IL IL22234A patent/IL22234A/en unknown
- 1964-10-14 GB GB41978/63D patent/GB1019786A/en not_active Expired
- 1964-10-16 US US404499A patent/US3355514A/en not_active Expired - Lifetime
- 1964-10-16 NL NL646412073A patent/NL141224B/en not_active IP Right Cessation
- 1964-10-16 CH CH1345164A patent/CH442743A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR1379756A (en) | 1964-11-27 |
| BE653912A (en) | 1965-02-01 |
| GB1019786A (en) | 1966-02-09 |
| DE1250120B (en) | 1967-09-14 |
| CH442743A (en) | 1967-08-31 |
| FR1406658A (en) | 1965-07-23 |
| NL141224B (en) | 1974-02-15 |
| LU47075A1 (en) | 1964-12-03 |
| NL6412073A (en) | 1965-04-20 |
| US3355514A (en) | 1967-11-28 |
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